Journal
SOLID STATE IONICS
Volume 365, Issue -, Pages -Publisher
ELSEVIER
DOI: 10.1016/j.ssi.2021.115656
Keywords
Lithium-ion conductivity; Mechanical milling; Complex hydride; Lithium alanate; Li-ion site disorder; Solid state NMR
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Funding
- JSPS KAKENHI [17K14827, 19K15304]
- Interuniversity Cooperative Research Program of the Institute for Materials Research, Tohoku University [18 K0075]
- Nanotechnology Platform and Project for promoting public utilization of advanced research infrastructure (Program for supporting introduction of the new sharing system) [JPMXS0420100520]
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The effect of mechanical milling on the lithium-ion conductivity of lithium alanate (LiAlH4) is investigated, showing significant improvement in conductivity by increasing the vacancy concentration at the Li-ion site of inner LiAlH4 grains.
The effect of mechanical milling on the lithium-ion conductivity of lithium alanate (LiAlH4) is investigated. Although pristine LiAlH4 is a poor ion conductor in its highly crystalline state, short-time mechanical milling for 0.1-2 h is shown to significantly improve the conductivity. Hand-milling treatment in an argon-filled glove box is also shown to improve the conductivity. The activation energy (E-a) for ion conduction of milled LiAlH4 is similar to 0.70 eV, which is attributed to Li-ion site vacancy-mediated conduction. However, the Ea of pristine LiAlH4 shows a large value of 0.84 eV. The Li-7, Li-6, Al-27 nuclear magnetic resonance and infrared spectra suggest that surface Li hydroxide species would exhibit Li-ion conduction in pristine LiAlH4. Thus, the milling treatment can eliminate the effect of surface hydroxide species and increase the vacancy concentration at the Li-ion site of inner LiAlH4 grains, which results in the enhancement of the conductivity.
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